Premium
Diastereoselective [4+2] Cycloaddition Reaction of 1‐Neomenthyl‐1,2‐diphosphole: Facile Synthesis of P ‐Chiral Cage Phosphines
Author(s) -
Zagidullin Almaz,
Miluykov Vasili,
Polyancev Fedor,
Latypov Shamil,
Sinyashin Oleg,
Lönnecke Peter,
HeyHawkins Evamarie
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500558
Subject(s) - chemistry , enantiopure drug , cycloaddition , aromaticity , maleic anhydride , enantiomer , delocalized electron , alkylation , medicinal chemistry , organic chemistry , enantioselective synthesis , catalysis , molecule , polymer , copolymer
3,4,5‐Triphenyl‐1‐(+)‐neomenthyl‐1,2‐diphosphole was obtained by alkylation of sodium 3,4,5‐triphenyl‐1,2‐diphosphacyclopentadienide with (–)‐menthyl tosylate. High delocalization within the planar heterocycle of the diphosphole is indicative of low aromaticity. Thus, the [4+2] cycloaddition reaction of this compound with maleic anhydride proceeded under mild conditions with high diastereoselectivity (up to 88 % de ) and resulted in the corresponding enantiopure 1,7‐diphosphanorbornadiene as an individual enantiomer. The observed high diastereoselectivity may be explained by thermodynamic control of the reaction.